Dark-blue monoazo dyestuffs.



' No Drawing;

' 4 is not limited to these examples:

- by addition or about kilos of Solvay t after thorough mixing, 7O kilosof Solvay ture does net rise above 20 C.- 'fllhe liquor,

.through green'to dark blueandafter a while deposits the greater part of the dye- '50 new-and useful Improvements in the Manutracedon brilliant yellow paper.

.of betanaphthoi in 30Q liters. ofwater andTO- attacke ,"luted'by addition of 1500lite rs of water aiid "STATES PATENT m snomer. Bfi'NIGER, or BASEL, -swzcrzaanmm,5assrenonr0 --cIiEia-Is c iri FAJBBIK vomzzALs SANDOZ, orgBAsEL, SWITZERLAND,- A conroaarron or swrrzsmlg'n para-nuns MoNoAZo1nYnsrurr's'1-" If specifications)! Lettcrsgatent, l

1,014,039; i epmic eoa'mca June a, 1911."'--Serla1lid-$31,892:

heated p-W 6.1% Bur a... solution thus' obtainedjfabout" 1 09" 16 hydrochloric acid of JB." the'jdyest recipitatedin "brown f "small needles ronz luster, which areffi l terjeflofii","pres and dried. Itfornis a'brownblack pow dissolving instrong sulfuric acid 'witliibl'de To-dll whomitlmay cozwc'rn.--

- Be it known that I, Msncmon Bernese, a citizen of-the, Swiss Repu'blic,-'rjesiding in Basel, Switzerland, havein ented-certain facture of Dark-Blue MonoazoDyestufis, of which the following is a specification. My invention relates to the manufacture "of dark blue monoazo dyestufis by combin ing the monobromnaphthalene-l-diazo-2. oxid-4-sulfonic acid, described in my application for Letters Patent, Serial N 0. 631,893 of'the same day, with phenol compounds, such as resorcinols, the. naphthols, dioxynaphthalenes andfnaphtliolsulfonic acids. They are characterized by the property, that their attierchrorhe'd dyeings are, of a more bloomy and abluer shade, being less altered-by-artificial light than those of the analogous non-brominated azo dyestuffs. The monobromnapht-halene-1-diaZo-2-oxid 4-sulfonic acid used'for. the manufacture of these new .monoazodyes can be obtained by treating with bromin at temperatures varying from 90 C. naphthalene-1-di'az0-2- oxidA-sulfonic acid dissolved inhighly. 001 centuated, monohydrate or weakly fuming sulfuric acid and in presence-of a halogen carrier such as iodin or dissolved in chlor sulfonic acid.

The following are examples to illustrate the nature of my invention, which, however,

O 'n addition ofalkali carbonatesorfaminm .nia the aqueous solutionmms e-' ueeb1 ;j='- caustic alkali's' change into "blue-red; Min-$5 eral acids precipitate the dyes'tuif "in" red brown fia'kesL- ltadye's on' non mofdanted" wool from an acid'bath brown-violet'shade's" which on subsequent chromi'ngi tu'rnfto' Hark 1 blue shadesoi excellent fastness to*'p( ttin "7O milling, carbonizing and light. The jdai lg blue dyeings'-.. obtained directl on chrome mordante'dswool are distinguished by the" .same valuable. properties. r Example-lliz Dissolve 40 kilos of alpha-. naphthol in 300 kilos of soda lye 30% at." 89 (1., cool down while stirring well to 10"?" G; and introduce in' about one hour by regular portions 82 kilos of finely. powdered -monobromnaphthalone 1 diazo 2 oxid- 4-sulfonic acid, 15. (3., being thereby not exceeded and workin all the time well through the rapidly tiickeniug mass by a strong malaxator. The combination is completed after somehours, a thick violet-black 85 paste being formed. soon as non-at tacked bronmaphthalene 1 dia z'o-2-oxid-4e sulfonic acid can no more'therein be traced, the product is dissolved in about 1000 liters of water and-the dyestu-fi isprecipitated in small brown black .bronze;s hining needles at 45--50 0., by neutralizing the free-alkali with about 200 kilos of hydmchloric ,acid of 21- Be. Pressed and dried itforms a Example I: 156 kilos of monobromnaphthalene-1 diazo-Z-oxid--sultonie acidaredissolved at 15 G. in 1500 liters of water soda, until a weakly alkaline reaction can be Into the solution'thus prepared a solutionoi 80-kilos boiling waterwith violet black color, turninto pure blue ona'ddition of alkali earbonates, while caustic alkalis change into blue. red. By mineralflacids'the dye-stufii is precipitated in violet brown flakes; it dissolves in strong sulfuric acid with greeni'sh' blue color, and" dyes on non-mordanter wool froma'n acid bath'brownish. violet I shades, whichon subsequent chroming change to a beautiful greenish blue black of excelle'n't fastness against potting, milling, .carbonizing and light. Q

Similar .dyeings are obtained directly-on kilos-of 33% caustic sodalye is run,- and-= soda dissol ed in' 300-:. liters' of; .water' is added, care being taken, thatthe temperawhich' is: at first-yellow changes rapidly h stuflfin smallbright blackish eencrystals, a thick aste bein fformed. 'soonas' und .diazosul onic .acidcan .no longer be with -resorcinol, the mass. is diin :boiling ':water with 'bIack vi let' cQIdri brown black powder, which dissolves in 95 1 'chrome mordanted wool from -a.'- boiling bath, rendered slightly acidby addition of acetic or formic acid.

In the foregoing examplesdhe naphtholscan .be' substituted by -resorcinol,-- by. dioxynaphthalenes and naphtholsulfomc acids, ortho-ox'y dyestuffs of similar p'roperties be -ing thereby obtained.-

The described process for the combination of themon'obromnaphthalene- 1. diazo 2- oxid-4-sulfonic acid may also be varied in different directions, ,as. toftemperetm'e, quantities and strength offthe' employed alkali Also suitable organic diluents' as 'alcohol,-' ani1in, pyridin, etc; may be em ployed, to accelerate'in an alkaline medium ';the reaction between the monobroninaphthalene-l diszo-2-oxid-4-sulfonic 'acid and the phenol compounds.

The reduction products'of the dyestuffsare monobrom 1' 7 amino-2-naphthol-4 sulfonic acid and an amidophenol-compound.

' 7 What I claim is: v

1. The process for the manufacture of. dark blue monoazo dyestufisfby' combining monobromna hthslene ;1"- diazo 2- oxid- 4-sulfonijc acid with phenol compounds.

process for the manufacture of- Z2 T darlifb ye monogzo dyestufi's by combining monobromna hthailene- 1 diezo 2 oxid- -4-sulfohib sc1d with nephthol compounds.

. 3. As new products, the monoazo dyestuffs derivedfrom monob'romnaphthalenel-diazo-2-oxid-4;.-sulfonici eci'dv ands-phenol compounds, which yield, violet to violet black solutions in boilingqwster, blue solutions in strong sulfuric acid and dye unmordanted-wool from an acid bath in brownishviolet shades, which on subsequent chroming turn to "dark blue.

4. As. new products, the monoazo dye stufi's derived from monobromnaphthalenel-diazo-2-oxidlr sulfonic acid and the naphthols'whic'h dissolve in strongsulfuric acid withblue, in boiling water with violetblack color, turning to pure blue on addition of 'alkali carbonates and-to'blue-red on addition of caustic elkelis and which dye unmordanted wool from an acid bath' in brownishviolet shades, changing into blue black by subsequent chroming.-l

In' testimony whereof, I have hereunto 'set my hand in the presence of two subscrib- 

